EP0701532A4 - Controlled release potassium divalent metal phosphate fertilizer - Google Patents
Controlled release potassium divalent metal phosphate fertilizerInfo
- Publication number
- EP0701532A4 EP0701532A4 EP94918065A EP94918065A EP0701532A4 EP 0701532 A4 EP0701532 A4 EP 0701532A4 EP 94918065 A EP94918065 A EP 94918065A EP 94918065 A EP94918065 A EP 94918065A EP 0701532 A4 EP0701532 A4 EP 0701532A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- potassium
- divalent metal
- percent
- phosphate
- aqueous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B17/00—Other phosphatic fertilisers, e.g. soft rock phosphates, bone meal
Definitions
- the present invention relates to agricultural mineral nutrients and methods for their preparation. More particularly this invention is directed to a new controlled slow releasing potassium divalent metal phosphate nutrient composition. This invention provides a new and effective method of preparing the new composition in the form of hard granules frqm caustic potassium/ divalent metal oxide powders, and acid phosphates.
- Potassium is one of the three plant macronutrients. Like nitrogen, moderate amounts of potassium can cause foliage and root burns on plants. Because of the high water solubilities of most potassium salts used as plant nutrients/ much of the potassium supplied as fertilizer is lost to leaching by rain or irrigation water.
- potassium is fixed so strongly in some water insoluble compounds that it does not solubilize, decompose, or release at rates fast enough to allow appreciable assimilation by plants even in a full growing season.
- Potassium metaphosphate, potassium aluminum silicate, and the naturally occurring micas are examples of potassium compounds which supply little potassium for assimilation as a plant nutrient in a single growing season.
- the compound potassium magnesium phosphate in the prior art has been reported as source of water insoluble potassium. Some prior art sources also report potassium magnesium phosphate as water soluble potassium. The prior art has reported the water insolubility of similar compounds wherein the magnesium moiety was substituted for by manganous, ferrous, cupric, cobaltous, and zinc moieties. Bassett and Bedwell, described the early preparation of potassium metal phosphates in "Studies of Phosphates - I,” Journ. Chem. Soc. (London) 1933, 854-871. They reacted aqueous soluble divalent metal salts with a large stoichiometric excess of dipotassium phosphate and dried the resulting product.
- a free flowing granular, non-burning, non-crumbling fertilizer composition consisting essentially of 55.5-69 percent coprecipitated and cogranulated magnesium ammonium phosphate, 6-8 percent magnesium potassium phosphate, 5-8 percent monoammonium phosphate, 13-20 percent monopotassium phosphate, 4-6 percent magnesium hydroxide, and 0.9-1.8 percent urea, was disclosed by C. C. Legal et al in U.S. Patent 3,585,020.
- the product was prepared by mixing aqueous urea and ammonia, aqueous magnesium hydroxide slurry and blending in a Pugmill with aqueous phosphoric acid, aqueous potassium hydroxide, water and recycled solids with water concentration maintained between 25 and 35 percent by weight.
- the wet fertilizer granules withdrawn from the Pugmill were then dried with air at a high temperature between 460 and 650 F.
- potassium divalent metal phosphates have been known for many years, and that the compounds contain the two nutrients most needed with slow controlled release properties for fertilizers.
- no quantitative control of the release of potassium, phosphorous, and divalent metals has been achieved. Therefore no commercialization has been made of this material which offers great promise in the field of agricultural nutrients.
- the prior art has supplied no teachings regarding quantitative control of the nutrients potassium, divalent metals, and phosphate from a single compound and has reported generally slow release of potassium, only from plant food mixtures, particularly from potassium magnesium phosphate admixed with magnesium ammonium phosphate.
- the preparation methods for the potassium divalent metal phosphates utilized in the prior art consisted of precipitation from aqueous solution or reaction in the form of a thick mass of solids and liquids including substantial recycle of solids in a Pugmill, followed by granulation in a rolling bed.
- the nitrogen system was adapted for use with potassium.
- total potassium was determined by Method 983.02, and the CWIK by 945.01, except that potassium was determined instead of nitrogen.
- HWIK and KAI were determined by the procedures of Method 955.05, except that potassium was analyzed instead of nitrogen.
- the Activity Index is sometimes referred to as Availability Index and is indicative of the availability of the water insoluble nutrient to a crop in a growing season.
- a 100 index indicates complete availability of the cold water insoluble nutrient in one growing season, and a 0 index indicates no availability in one season.
- Official Method 965.09 provides a method of determining minor nutrients in fertilizers and specifically the divalent metals calcium, copper, iron, magnesium, manganese, zinc, and cobalt. Availabilities in the soil of these metals may be determined by measurement of the solubility of the metals in ethylenediaminetetraacetic acid (EDTA).
- EDTA ethylenediaminetetraacetic acid
- a primary object of this invention is to provide particulate controlled slow release potassium plant nutrient composition which causes no damages to plant foliage or roots when applied at high rates but releases its potassium nutrient throughout one growing season.
- a further primary object of this invention is to provide a granular controlled slow release potassium divalent metal phosphate composition comprising water insoluble plant nutrients potassium, divalent metals, and phosphorous which are released in one growing season.
- a further primary object of this invention is to provide an effective method of preparing a water insoluble potassium divalent metal phosphate composition which effectively releases its agricultural nutrient contents in a controlled slow manner.
- a new solid, particulate potassium divalent metal phosphate agricultural nutrient composition which safely, slowly, and effectively releases its nutrients in a controlled manner, comprising potassium, divalent metal, and phosphate moieties in about a 1/1/1 molecular ratio with between 35 and 98 percent of each of its nutrient components insoluble in cold water.
- Other properties found essential to the effective composition include: an Activity Index (KAI) between 20 and 85 for the cold water insoluble potassium, a neutral ammonium citrate solubility for the phosphate between 35 and 85 percent, and a solubility in aqueous ethylenediaminetetraacetic acid for the divalent metal nutrient between 35 and 98 percent. Only when the composition was within the above parameters did it provide controlled slow release of its nutrient components in a single season.
- KAI Activity Index
- the new particulate agricultural nutrient composition could be effectively prepared by a new method from a homogeneous liquid comprising divalent metal oxide powder, concentrated aqueous caustic potassium, and concentrated aqueous acid phosphate, which with intensive mixing, quickly reacts exother ically to form homogeneous damp-dry solid particles of water insoluble potassium divalent metal phosphate at a temperature near to, or higher than, the boiling point of water.
- a molecular ratio of potassium/divalent metal/phosphate of about 1/1/1 with the divalent metal supplied as powdered solids, the potassium as concentrated aqueous caustic potassium, and the phosphate supplied as concentrated aqueous acid phosphate. It is necessary that the initial reaction mixture contain between about 25 and 50 percent by weight water and that a maximum reaction temperature of between 85 and 150°C be reached during a reaction-solidification time amounting to between 3 and 30 minutes, to provide a final product exhibiting a pH between 6 and 8.
- a new homogeneous particulate solid potassium divalent metal composition has now been discovered which provides controlled slow release of its components as effective nutrients for agriculture.
- the effective composition comprises potassium, divalent metal, and phosphate moieties combined in a molecular ratio of about 1/1/1, respectively.
- the cold water insolubility of each nutrient amounts to between 35 and 98 percent
- the cold water insoluble potassium has an Activity Index (KAI) between about 20 and 85
- the phosphate exhibits a neutral ammonium citrate solubility between 35 and 85 percent
- the divalent metal exhibits a solubility in aqueous ethylenediamine tetraacetic acid between 35 and 98 percent in the effective composition.
- the composition provides agricultural nutrients effective for plants.
- Divalent metals those metals having a positive valence of two and reacting on ratio with two negative valences, are the only metals suitable for the present composition. Those metals which are particularly effective in the composition are magnesium, manganese, iron, copper, cobalt, and zinc.
- the preferred plant nutrient composition is a hard granular potassium divalent metal phosphate which provides controlled slow and substantially complete release of its nutrients in one growing season. This composition contains nutrients, potassium, divalent metal, and phosphate in a molecular ratio closely controlled to 1/1/1.
- the cold water solubility of each nutrient is between 45 and 85 percent
- the KAI of the cold water insoluble potassium is between 45 and 85
- the neutral ammonium citrate solubility of the phosphate is between 60 and 85 percent
- the solubility of the divalent metal in aqueous ethylenediamine tetraacetic acid is between 60 and 95 percent.
- the preferred divalent metals are magnesium, manganese, iron, copper, and zinc.
- a practical method was discovered for the effective preparation of the solid particulate agricultural nutrient composition from a homogeneous liquid.
- a divalent metal oxide powder, aqueous caustic potassium, and aqueous acid phosphate moieties in a respective molar ratio of about 1/1/1 are admixed to form a homogeneous liquid initially containing between 20 and 50 percent water. While intensively mixing the homogeneous liquid, the aqueous moieties are reacted exothermically until a maximum reaction temperature between 85 and 150 C is reached.
- the reaction is continued with intensive mixing while moisture is evaporated from the homogeneous liquid for between 3 and 30 minutes until damp dry, water insoluble potassium divalent metal phosphate particles are formed which have a near-neutral pH of between 6 and 8 and cold water insolubilities of each nutrient between 35 and 95 percent.
- the method is operated preferably with the divalent metal oxide powder comprising particles with diameters smaller than 0.5 millimeter. Although the method operates most effectively with dry metal oxide powders, it is possible to successfully operate the method where the oxide powders are hydrated to their hydroxide form prior to reaction.
- aqueous caustic potassium sources such as basic potassium phosphates or potassium carbonates may be used in the instant method
- the preferred aqueous caustic potassium source is liquid potassium hydroxide at a concentration between 40 and 60 percent.
- aqueous acid phosphates may be used in the present method, such as potassium acid phosphate, and concentrated liquid phosphoric acids containing between 40 and 75 percent P 2 ° 5 * ⁇ he Phosphoric acids selected may be green or black wet process acids or white furnace acid. Either ortho-, pyro-, or poly- phosphoric acid may be used effectively in the method. Commercial superphosphoric acid containing a combination of ortho-, pyro-, and polyphosphoric acids is particularly effective when its P 2 ° e concentration is between 58 and 80 percent.
- the composition of the homogeneous liquid formed is an important aspect of the present method, and an initial water concentration between 22 and 35 percent is important.
- water concentrations are lower than 22 percent, reaction is incomplete and water insolubilities, particularly of the potassium component, are lower than required in the new composition.
- water concentrations are higher than 35 percent, the exothermic heat of reaction is insufficient to evaporate sufficient water to form the particulate damp dry solids required and the reaction mixture remains a liquid or a viscous semisolid without application of external heat.
- the reaction is continued while moisture is evaporated preferably for between 7 and 15 minutes until damp dry water insoluble potassium divalent metal phosphate particles are formed which contain between 8 and 18 percent water, and provide particles with optimum physical integrity, particularly resistance to crushing and abrasion.
- the particles may be dried further in an additional drying step to reduce moisture concentration to between 1 and 8 percent to provide maximum nutrient concentrations without reducing the physical integrity of the particles.
- the exothermic reaction is continued with intensive mixing while moisture is evaporated from the homogeneous liquid for between 7 and 15 minutes until hard, damp dry, water insoluble potassium divalent metal phosphate granules are formed which exhibit a near neutral pH of between 6.5 and 7.5.
- the homogeneous hard granules of potassium divalent metal phosphate fertilizer composition prepared by the instant method provide storage stability, attrition resistance, and controlled slow and complete release of nutrients heretofore unavailable from other potassium fertilizers.
- the method of this invention is effective primarily for the preparation of pure or agricultural grade potassium divalent metal phosphate and is not particularly effective when the potassium moiety is present in appreciably higher molar amounts than the divalent metal and phosphate moieties.
- the method may be effectively used to prepare a controlled slow release granular matrix fertilizer when the fertilizer contains between 0 and 80 percent additional plant nutrients homogeneously included in a matrix of potassium divalent metal phosphate.
- divalent metal oxide powder particles with diameters smaller than 0.5 millimeters, aqueous potassium hydroxide at a concentration between 42 and 50 percent, phosphoric acid containing between 48 and 71 percent P.Oe and additional plant nutrient powder amounting to between 20 and 80 percent of the final matrix fertilizer are mixed, so that potassium, divalent metal, and phosphate are present in a 1/1/1 molar ratio and water concentration in the homogeneous aqueous liquid formed is between 22 and 35 percent.
- the potassium, divalent metal, and phosphate moieties in the homogeneous liquid and additional plant nutrient powder are exothermically reacted and the additional plant nutrients are substantially unreacted while intensive mixing continues at a maximum temperature between 115 and 135°C.
- the additional plant nutrient powder are homogeneously included in damp dry controlled release plant nutrient granules.
- the homogeneous matrix fertilizer composition granules prepared by the instant method are hard and resistant to attrition and surprisingly release the additional nutrients included in the matrix at a controlled rate so long as the additional nutrients amount to between 20 and 80 percent of the composition.
- the rate of release of these added nutrients depends substantially on the amount added, with release rate increasing as the amount of added nutrients increases.
- Plant nutrients which may be effectively included as part of the composition of this invention include isobutylidene diurea, methylene urea, crotylidene diurea, urea, methylolurea, ureaformaldehyde polymers, and ammonium sulfate.
- This example illustrates the new composition by providing specific analyses and properties and relating them to the effectiveness of their agricultural nutrients.
- a hard granular potassium divalent metal phosphate plant fertilizer composition was prepared from concentrated potassium hydroxide, anganous oxide powder, and concentrated black orthophosphoric acid, which contained potassium, the divalent metal manganese, and phosphate in a molecular ratio of about 1/1/1.
- the granules were analyzed by AOAC methods and the results are listed as follows:
- the nutrient release properties of the potassium manganese phosphate granules were determined by long term leach tests carried out by incorporating the fertilizer granules in pine bark-sand filled pots, such as those used to grow ornamental plants like azaleas. The pots were watered to maintain optimum growing conditions and then drenched each week with water amounting to twice the pot free volume. The leachates were recovered and analyzed for potassium content. The tests included for comparative evaluation sulfur coated potassium sulfate-urea granules and plastic coated 18-6-12-Osmocote 9 month product. The results are tabulated as follows;
- the pots were analyzed for retained potassium after 40 weeks, considered to be a long growing season.
- the potassium solubilization from the sulfur and plastic coated products were found to be complete with virtually none of the potassium remaining undissolved.
- the potassium remaining from the potassium magnesium phosphate after a growing season amounted to 4.6 percent of the original material.
- Manganese and phosphate recovered in the remaining pine-bark sand of the potassium manganese phosphate amounted to 12 and 7 percent, respectively, of the original amounts.
- This example uses the widely accepted measurement of Osmolality as an indicator of scorching and phytotoxicity to plant roots and foliage by plant nutrients. Measurements were made of Osmolality as mmol/Kg on 3 percent K_0 concentrations in water. Tests were made by measuring the osmolalities of ground
- This example demonstrates a preferred embodiment of the method of the instant invention for preparing potassium divalent metal phosphate as hard granular fertilizer for controlled slow release as plant nutrients.
- the device in which the preparation was performed consisted of an inclined vertical rotary steel pan 0.72 meters in diameter, 0.38 meters deep, with the pan rotating at an angle of 30° from vertical.
- the pan was equipped with a stationary wall scraper-deflector which deflected the contents of the pan toward a high speed rotor 0.35 meters in diameter located 6 centimeters above the bottom of the pan so that its tips pass 3 centimeters from the wall of the pan.
- the rotor consisted of a 7.5 centimeter diameter shaft with 7 steel bars 2 centimeters thick and 5 centimeters wide, protruding radially equi-spaced therefrom starting at the bottom of the shaft with each additional bar located 3 centimeters above the next lower bar.
- the mixture was exothermically reacted in the homogeneous liquid until a maximum reaction temperature of 122 C was reached.
- the reaction was continued with intensive mixing while moisture was evaporated from the homogeneous liquid for 6.5 minutes until damp dry, water insoluble potassium magnesium phosphate granules were formed.
- the damp dry granules contained 13.5 percent moisture and pH was measured to be 7.0. These granules were then dried in a fluid bed dryer with hot fluidizing air at a temperature of 200°C until the moisture of the granules was reduced to 6.6 percent.
- This example is provided to demonstrate the effectiveness of the method with the a photeric divalent metal zinc and furnace grade phosphoric acid.
- Zinc oxide powder 72 percent Zn 20.8
- the homogeneous liquid provided potassium, zinc, and phosphate at a molecular ratio of 1/1/1 with a water content of 33.6 percent. Exothermic reaction of the liquid provided a maximum temperature of 119 C and was continued with intensive agitation while moisture was evaporated for 9.4 minutes until damp dry water insoluble potassium zinc phosphate granules were formed. These granules were dried from 21 percent to 2.2 percent moisture, and analyses made are listed as follows: Chemical Analysis Percent
- This example demonstrates the effectiveness, controlled slow release, and safety of the composition of this invention as a plant nutrient source.
- Example 3 The product of Example 3 was applied to separate triplicated 6 foot by 6 foot plots of irrigated mature Tall Fescue grass at potassium rates of 3 pounds K ⁇ O per 1000 square feet. The nitrogen was supplied as IBDU (50%) and urea (50%). A single application was made to the plots and observations were made of Turf Quality for a period of a 12 week growing season. Turf Quality was rated 9 for hardy green, and 0 if brown, with numerical gradations for qualities between. The results are tabulated for the Example 3 granules and other particulate commercial potassium fertilizer materials as follows:
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US64718 | 1993-05-19 | ||
US08/064,718 US5374294A (en) | 1993-05-19 | 1993-05-19 | Controlled release potassium divalent metal phosphate fertilizer |
PCT/US1994/005699 WO1994026660A1 (en) | 1993-05-19 | 1994-05-19 | Controlled release potassium divalent metal phosphate fertilizer |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0701532A1 EP0701532A1 (en) | 1996-03-20 |
EP0701532A4 true EP0701532A4 (en) | 1997-10-08 |
EP0701532B1 EP0701532B1 (en) | 1999-09-15 |
Family
ID=22057837
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP94918065A Expired - Lifetime EP0701532B1 (en) | 1993-05-19 | 1994-05-19 | Controlled release potassium divalent metal phosphate fertilizer |
Country Status (13)
Country | Link |
---|---|
US (1) | US5374294A (en) |
EP (1) | EP0701532B1 (en) |
JP (1) | JPH09505021A (en) |
AU (1) | AU684290B2 (en) |
BR (1) | BR9406543A (en) |
CA (1) | CA2161553C (en) |
DE (1) | DE69420724T2 (en) |
ES (1) | ES2135583T3 (en) |
FI (1) | FI955569A (en) |
IL (1) | IL109662A (en) |
NO (1) | NO310681B1 (en) |
PH (1) | PH30812A (en) |
WO (1) | WO1994026660A1 (en) |
Families Citing this family (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU778813B2 (en) * | 1996-12-17 | 2004-12-23 | Michael Markels Jr. | Method of increasing seafood production in the barren ocean |
FI117973B (en) * | 2001-04-17 | 2007-05-15 | Kemira Growhow Oyj | Improved forest fertilizer |
US6451361B1 (en) * | 2001-05-29 | 2002-09-17 | Agri-Nutrients Technology Group, Inc. | Alkali metal magnesium phosphate hydrate buffering feed mineral |
US7052581B2 (en) * | 2001-08-01 | 2006-05-30 | Philip Morris Usa Inc. | Process of producing magnesium ammonium phosphate in monohydrate form (dittmarite) |
US20050279475A1 (en) * | 2004-01-30 | 2005-12-22 | Philip Morris Usa Inc. | Processes of making monohydrate form of magnesium ammonium phosphate and processes of making cigarette paper using same |
WO2010089776A1 (en) * | 2009-02-03 | 2010-08-12 | Chandrika Varadachari | Micronutrient fertilizers and methods of making and using the same |
US9181137B2 (en) | 2009-03-20 | 2015-11-10 | Agtec Innovations, Inc. | Micronutrient fertilizers and methods of making and using the same |
AU2011288134B2 (en) | 2010-08-10 | 2014-02-27 | Agtec Innovations, Inc. | Phosphate fertilizers and methods of using the same |
US8999031B2 (en) | 2010-08-10 | 2015-04-07 | Agtec Innovations, Inc. | Polyphosphate fertilizer combinations |
IL220686A (en) * | 2012-06-28 | 2017-05-29 | Rotem Amfert Negev Ltd | Continuous process for manufacturing freely flowing solid acidic p/k fertilizer |
BR112017007512B1 (en) | 2014-10-15 | 2022-09-27 | Liquid Fertiliser Pty Ltd | METHOD FOR PREPARING A FLOWING LIQUID FERTILIZER, AQUEOUS DISPERSION AND METHOD FOR APPLYING A ZINC PHOSPHATE AS A PLANT FERTILIZER |
US11643370B2 (en) | 2014-10-15 | 2023-05-09 | Liquid Fertiliser Pty Ltd | Stable aqueous dispersions of zinc phosphates |
EP3359509A4 (en) * | 2015-10-08 | 2019-06-19 | Liquid Fertiliser PTY Ltd. | Aqueous dispersions of potassium calcium polyphosphate |
CN106831273B (en) * | 2017-01-24 | 2021-03-16 | 北京金都园林绿化有限责任公司 | Special organic fertilizer rod for garden trees and using method |
US10820588B2 (en) | 2018-08-24 | 2020-11-03 | Wisconsin Alumni Research Foundation | Compositionally and morphologically controlled nanostructures for delivery of micronutrients and suppression of disease in agriculture |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1924284A1 (en) * | 1969-05-13 | 1970-11-19 | Mueller Dr Frank | Sodium or potassium magnesium phosphates of - high water insolubility |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3285731A (en) * | 1963-07-22 | 1966-11-15 | Grace W R & Co | Magnesium potassium phosphate-containing fertilizer and process |
US3585020A (en) * | 1968-12-11 | 1971-06-15 | Grace W R & Co | Nonburning fertilizer composition |
DE2831672C3 (en) * | 1978-07-19 | 1981-02-12 | Kali Und Salz Ag, 3500 Kassel | Process for the production of potassium magnesium phosphate |
DE3914796C1 (en) * | 1989-05-05 | 1990-05-17 | Kali Und Salz Ag, 3500 Kassel, De |
-
1993
- 1993-05-19 US US08/064,718 patent/US5374294A/en not_active Expired - Lifetime
-
1994
- 1994-05-17 IL IL10966294A patent/IL109662A/en not_active IP Right Cessation
- 1994-05-18 PH PH48295A patent/PH30812A/en unknown
- 1994-05-19 EP EP94918065A patent/EP0701532B1/en not_active Expired - Lifetime
- 1994-05-19 AU AU69547/94A patent/AU684290B2/en not_active Ceased
- 1994-05-19 WO PCT/US1994/005699 patent/WO1994026660A1/en active IP Right Grant
- 1994-05-19 ES ES94918065T patent/ES2135583T3/en not_active Expired - Lifetime
- 1994-05-19 CA CA002161553A patent/CA2161553C/en not_active Expired - Lifetime
- 1994-05-19 DE DE69420724T patent/DE69420724T2/en not_active Expired - Fee Related
- 1994-05-19 BR BR9406543A patent/BR9406543A/en not_active Application Discontinuation
- 1994-05-19 JP JP6525823A patent/JPH09505021A/en not_active Ceased
-
1995
- 1995-11-16 NO NO19954630A patent/NO310681B1/en not_active IP Right Cessation
- 1995-11-17 FI FI955569A patent/FI955569A/en unknown
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1924284A1 (en) * | 1969-05-13 | 1970-11-19 | Mueller Dr Frank | Sodium or potassium magnesium phosphates of - high water insolubility |
Also Published As
Publication number | Publication date |
---|---|
FI955569A0 (en) | 1995-11-17 |
CA2161553C (en) | 2001-07-10 |
AU6954794A (en) | 1994-12-12 |
AU684290B2 (en) | 1997-12-11 |
NO310681B1 (en) | 2001-08-13 |
US5374294A (en) | 1994-12-20 |
EP0701532B1 (en) | 1999-09-15 |
CA2161553A1 (en) | 1994-11-24 |
DE69420724T2 (en) | 2000-04-06 |
NO954630L (en) | 1995-11-16 |
FI955569A (en) | 1995-11-17 |
NO954630D0 (en) | 1995-11-16 |
JPH09505021A (en) | 1997-05-20 |
PH30812A (en) | 1997-10-17 |
WO1994026660A1 (en) | 1994-11-24 |
EP0701532A1 (en) | 1996-03-20 |
ES2135583T3 (en) | 1999-11-01 |
BR9406543A (en) | 1996-01-02 |
DE69420724D1 (en) | 1999-10-21 |
IL109662A (en) | 1999-11-30 |
IL109662A0 (en) | 1994-08-26 |
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